Disulfide ring compounds and polymerization thereof



Patented Oct. 27, 1 953 UNITED STATES PATENT OFFICE 2,557,198 DISULFYIDEBING COMPOUNDS AND PoLYMcRrz-ATIoN THEREOF Franklin 0. Davis, *Trenton, N. J., assignor, by mesne assignments, to Reconstruction Finance Corporation, Washington, D. 0., a corporation of the 'UiiiteTSta'tes" No Drawing. Application August *2, I951,

SerialfNo. 240,067

1 Claim. "(CL 260-79.1)

tlated eases of simple heterocyc'lics containing disulfide groups in the 'rings and no indications of the novel properties of such heterocyclic compounds.

There are many advantages in substances which without the necessity of solvents or dispersion media can :be made, stored, and transported in the form .of a liquid and which can be converted when desired from'the liquid condition into a high polymer having rubbery 'or other useful characteristics. It is gfurther advantageous when such liquids can be so converted by a process of true polymerization, as distinguished from condensation, because then the polymerization can be effected without the large change inyolume' and density which accompaniescondensation reactions. Such physical changes are frequently accompanied by cranks and other flawsin' the resultant casting. A liquid having the above-mentioned characteristics is a useful casting compound because it can be poured into a mold, will readily fill the spaces and interstices therein and can then, without large shrinkage, be converted into a solid molded producthaving rubbery or other useful'characteristics.

The outstanding properties of the polysulfide polymers in respect to solvent resistance are well known and their usefulness for many applications is unquestionably valuable; The desirability and usefulness of such polymers when obtained from liquids isclearly demonstrated by the various liquidpolysulfide polymers now available. These liquid polymers while advantageous in many respects, still require curatives generally ih stoichiometric or larger amounts in order to be convertedinto a polymer by oxidation of thiol to djsulfide groups. The low molecular weight liquids f. this invention, on the other hand, are converted to solid rubbery or plastic polymers by use of only's'mall, catalytic quantities, of converting materials. It is thus obvious that these materials possess many advantages not present in the line of liquid polymers, now available, which are capable of conyersion to the polysulfide polymers. Previous to "the triercaptan liquid polymers the only way'of'o'btaining these polymers was by the reaction of halide and polysulfide resulting in an "aqueous iatexbr suspension, offering numerous disadvantagesdn many instances. The liquid compounds of this invention present advantages over the thiol terminate iiqui p y e ha e a mu less viscous'and e "'eiitheless capableoffconru e eadi o shrb mf hey ar fact, the only true mQl1;01' !1' er S of thejl qlysulfide type ofpolymer."

Generically the invention comprises new compositions of matter responding to generic formula their production and polymerization. The general formula; of a preferred class of said cyclic disulfides is prising and would not be expected from the chemical structure of the compounds. The organic aliphatic iiisulfides, either monomeric or polymeric; are quite stable compounds.

The presentinyention provides new compounds responding to" the above criteria, methodso'f polymerizing them and methods for producing .w\.,.t. .i i

In accordance with the invention, monomeric ringcompou-nds are produced and polymerized,

amp o s monomer r ns m qunds b ing those having the following structures:

R s om-o EI-CHz Example 1.-Polymerization of Compounds 1, 1A, and 1B 100 cc. of the cyclic dithiodiethyl oxide (Compound 1 above), which is an oil at room temperature, are mixed at room temperature, e. g. C. with 2 cc. of a 25 per cent solution of sodium methylate in methanol and the mixture is poured into a mold. Polymerization begins immediately without heating and in about 24 hours a rubbery polymer is obtained which becomes tough in about e8 hours. Heat is evolved during the reaction i. e. the reaction is exothermic.

Example 2.Polymerization of Compounds 1, 1A, and 1B Proceed as in Example 1 using 10 cc. of the sodium methylate solution. The polymerization proceeds faster and a tough rubber is obtained within a few minutes.

Example 3.Polymeri2ation of Compound; 2, 2A, and 2B Proceed as in Example 1 using the dithiodiethyl sulfide (Compound No. 2) instead of the dithiodiethyl oxide. A horn-like polymer is obtained. This reaction is much slower than that shown in Example 1.

Example 4.Polymerieation of Compounds 3, 3A, and 3B To 3.00 cc. of the cyclic dithiodiethyl formal (Compound 3 above) are added 5 cc. of water which is stirred in thoroughly to disperse the water in the cyclic formal. Polymerization proceeds spontaneously without the necessity of heating and is completed in about 48 hours. The polymer is a soft rubbery material.

Example 5.-Polymerieation of Compounds 4, 4A, and 4B Proceed as in Example 4 substituting the cyclic dithiodiethyl thioformal (Compound No. 4) for the clithiodiethyl formal. This reaction is much slower than that with the corresponding oxygen monomer.

Example 6.Polymerization of any of the above mentioned cyclic disulfides cc. of any of the above-mentioned cyclic disulfides e. g. Compound 1 are mixed with 5 cc. of a ten per cent solution of NaSI-I in absolute ethyl alcohol. Polymerization begins immediately without heating and in about 2 hours a solid high polymer is obtained.

Example 7.P0lymerteation of any of the above mentioned cyclic disulfides Proceed as in Example 6 using 5 cc. of a 10 per cent solution of NazS in absolute ethyl alcohol as catalyst.

Example 8.-Po-Zymerization of any of the above mentioned cyclic disulfides Proceed as in Example 6 using a catalyst 5 cc. of a 10 per cent solution of NaZSI Where x is a number (fractional or whole) greater than 1 and not greater than 6.

Example 9.Polymerieation of any of the above mentioned cyclic disulfides Proceed as Example 6 using as catalyst 5 cc. of a 10 per cent solution of benzyl trimethyl ammonium butoxide in butanol.

mew, 19s

' lrocec as inExammeu' ineas ca .9.

PtdiethyIcin -tn m n Example 11 F Polg merizatz'on of 'C'ompotmds =1,

IA, and 1:3

.130 one liter of water containing V2 ,mol. .of NflzSi. 10 .vccfis, of ya, ,per cent. solution .of. sodium saltpf alkyl naphthalenesulfonic acidandadispcrsion of magnesium hydroxide prepared .by the interactionof, 50 ccfis of a.,50 per cent MgCh 51-1 0 9.11150 ccfspfa 20 per: centh solution oi in ,watergare, added. 'II11is;-.miXture is. heated. to 18021 and. there is added. slowly loo grams of Compound 1. This is heated for 30 n 1 inut es at 180 F. then the polysulfide solution is washed out and the. latex. when-freeiof-polysulfide i coagulatemby acidification. It gives a polymer-closely resembling a polymer prepared: .in -:Examp1e A below \butnot. contaminated-with thioxane or the. other impurities which may be present from the original reaction.

Example12.P0Zymerieation of a. mixture of Compounds 1 and 2 Proceedflas in Exarnple zusing, a mixture of 50 cc. of .Compound..#l.and 50cc. of Compound #2. ,Inthis .case a fairly. rapid polymerization takesplace. 'I'he,produc't;is a co-polymerhaying rubbery.,properties. which: is I composedofequimolecular proportions of thioether and: ether disulfides. Latices of thesetypes, if miiged wo uld not give co-polymers unless given a polysulfide treatment.

A- variety -ofcatalysts may be used -including alkali alcoholates and alkalinesulfides, hydrosulfides 'and-polysulfides; e. g; the-sulfides-,--hydrosulfides and =polysulfides ofsodium,; potassium, ammonium,-ca1cium, barium etc. ---Even water alone acts as acatalyst as 1 illustrated Joy-Examples 4 and 5.

Other-classes. ofimaterials which can .be. reflectiyely. used as catalysts are those. of. the, r up consisting of alkyl andaralkylsubfitituted amnionia compounds, and alkyl. and aralkyl substituted ammoniumcompounds. Examplespf thosecompounds areas iollows .A .yl and paralkyl substitutedammonia compounds lemmas) 1 i NG l'liM iczH N Diethyiene triami-ne on,- {3H1 0H,- CH--NH1 O Ha- CHA C hex lamine (HOCzI-IQ 3N '-Trlethanol amine H2NQ2H4NHC2H4NHC2H4NHC2H4NH2 Tetraethylene pentamine CH3 (HOCzI-IQeN 1. Methyl diethanol. amine C4Hg (HOCzHg) 2N Butyldiethanol amine CHflf-N OH:

I CH2 N- 1CH2' N Hexamethylene tetramine Ethylene diamine :H NC HMC WNHQHQH Triethylene tetramine 2. 'Alkyl and aralkyl substituted I ammonium compounds.

I C2H5)4 NOC3H5 mmi ei nmet i (CH3)4NQC4H9 Tetramethyl ammonium butoxide CsHsCHz (C2H5 )sNOCsHs Benzyl triethyl ammonium blltoxide CcHsCHz C2H5) (CH3) aNIOCaHs Benzyl dimethyl ethyl ammonium butoxide (CH3) 4NOC2H5 Tetramethyl ammonium ethoxide (Gil-I9) 4NQC4 H9 Tetrabntyl ammonium butoxide CsH5CI-I2 C4H9 3NOC4H9 'Benzyl tributyl ammonium butoxide CcHsCHz (C4H9 CzHs) CH3 NOC4H9 Me thylethyl butyl henz yl ammonium b utox ide HOC2H4NH3OH Monoethanol ammonium hydroxide (HOCzhLQzNHzOH n l am ee l we e? (HOC2H4) sNI-IQH Triethanol ammonium hydroxide H3NO2H4NH3 9 s mo u mm HalTTOrHiNHQzHilq fia OH OH .Diethyleneamino bis ammonium hydroxide Ammonia can also be. used as a catalyst.

The. amount of catalystusedmay vary trom a very srpall amount, say 0.05% .to a quite large amount, the maximum being dependent on the physical properties desired in ,the final polymer. Large amounts of .catalystswillincrease the polymerization rate, but will, of coursenemaininthe polymer and thus afiectthe properties. The preferred range is 1 to 10 of catalyst based on the amount of cyclic compound used,

Very little is known of the mechanism of this polymerization, but it is, in the final result, the conversion. 01! acyclic monomer to a linear polymenaccording totheequation S 7 catalyst I ing to and openingihe-ring.by-breaking the link between the sulfur atoms. The product which may be momentarily a free radical bran ion, can then recombine to givethe original starting material, or canreact with another selenium to give a polymer with elimination of the catalyst or its conversion to sometype of'terminal group. In=view of the high polymeric'nature or the product, it isthought that the catalyst i eliminated for'the most part from the molecule.

-Instead-of polymerizing a-single cyclic disulfide,

mixtures of 2 or moreof said'cyclicdi'sulfides may As is well known, linear polymers having repeating polyalkylene disulfide units may be made by reacting polyakylene polyhalides with alkaline polysulfides e. g. the'polysulfides of the alkali and alkaline earth metals and ammonium. The alkaline polysulfides include the disulfides, trisulfides, tetrasulfides, pentasulfides and hexasulfides. The resulting linear polymers are composed of repeating units having the general formula --RSS and to the sulfur of the above shown disulfide linkage, labile or isosulfur may also be attached.

Said linear polymers may also be made by oxidizing polymercaptans, as is also well known. See for example Patrick Patents 2,216,044, September 24, 1940, and 2,142,145, January 3, 1939.

A theory of the formation of the ring compounds is that during steam distillation of the chain polymers, some of the units thereof break off and form cyclic compounds by union of terminal sulfur atoms of said units. The mechanism of the ring formation is not known but is such that ring formation and elimination ap- A pears to regenerate the group so that the reaction acts in a chain mechanism and does not diminish until the polymer is substantially gone, or until a monosulfide or other non-labile group is encountered in the chain.

The following examples illustrate the abovementioned method of making the ring compounds i. e. the cyclic disulfides.

EXAMPLE A.PRODUCTION OF COMPOUND 1 Three mols, for example, 972 cc. of 3.09 molar N2.2S4.27 was treated with one gram of the sodium salt of butyl naphthalene sulfonic acid, eight grams of sodium :hydroxide and 25 grams of MgClz 6H2O all used as approximately 25 per cent solutions. This reaction mixture was heated to a temperature of 140 F. and there was added tothis reaction mix 2.? mols (386 grams) of The feed period was 90 minutes during which a latex formed in. the reaction. This latex was distilled with steam until 1000 cc. of distillate had been collected in order to remove all of the congeneric 1,4-thioxane formed in the reaction.

After one washing the latex was treated with 4.5 mols (180 grams) sodium hydroxide for one hour at 180 F. The latex was washed free of polysulfide solution and subjected to steam distillation. The distillate in this case was cloudy with droplets of oil settling out. Decantation gave approximately 1 grams of oil per 500 cc. of distillate but this amount could be somewhat increased by extraction with ethyl ether. Although the rate of formation of the oil, as evidenced by its rate of removal in the steam distillation, was quite slow, it continued practically unchanged for a considerable period of time, for example, about two months of distillation. If other halides are used other polymers are obtained which give different cyclic materials having diiferent physical properties and difierent degrees of stability. To produce Compound 1A, proceed as above using dichloro methyl ether instead of his B-chloroethyl ether. To produce compound 1B proceed as above using bis,(gamma chloro propyl) ether.

EXAMPLE B.PRODUCTION OF COMPOUND 2 Proceed as in Example A except instead of 386 grams of dichloro-ethyl ether use 429 grams of C1C2H4SC2H4C1 and proceed as before. To produce Compounds 2A and 2B, proceed as above using bis(chloromethyl) thioether and bis(gamma chloropropyl) thioether.

EXAMPLE C.-PRODUCTION OF COMPOUND 3 Proceed as in Example A using instead of dichloroethyl ether 467 grams of his beta chloroethyl formal C1C2H4OCI-I2OC2H4C1 and proceed as before. To produce Compound 3A proceed as above using bis(chloromethyl) formal instead of his beta chloroethyl formal. To produce 33 proceed as above using bis(gamma chloropropyl) formal.

EXAMPLE D.PRODUCTION OF COMPOUND 4 Proceed as in Example C using equimolecular proportions of bis beta chloroethyl thioformal ClCzI-LrSCHzSCzHrCl instead of the formal of Example C. To produce Compound 4A proceed as above using bis(chloromethyl) thioformal instead of bis beta chloroethyl thioformal. To produce 4B proceed as above using bis(gamma chloropropyl) thioformal.

EXAMPLE E.-PRODUCTION OF COMPOUND 5 Proceed as in Example A using instead of dichloroethyl ether 505 grams of triglycol dichloride C1C2H4OC2H4OC2H4C1 and proceed as before. To produce Compound 5A proceed as above using bis(chloromethoxy) ethane instead of dichloroethyl ether. To produce 5B proceed as above using bis(gamma chloropropoxy) ethane.

EXAMPLE F.PRODUCTION OF COMPOUND 6 Proceed as in Example E using equimolecular proportions of the compound bis (beta chloroethyl thio) ethane C1C2H4SC2H4SC2H4C1 instead of the bis (beta chloro ethoxyethane) of Example E. To produce Compound 6A proceed as above using 1,6 dichloro 2,5 dithiaheXa-ne instead of bis beta chloro ethoxyethane) To produce 63 proceed as above using 1,10-dichloro-4,'7, d'ithiadecane.

EXAMPLE G.PRODUCTION OF COMPOUND 7 Proceed as in Example A using equimolecular proportions of 1,5 dichloro n-pentane instead of the dic'hloroether of Example A and using the same proportions of Nassau in the form however of a 1-molar solution in isopropanol. To produce Compound 7A proceed as above using trimethylene dichloride instead of dichloroether. To produce 7B proceed as above using heptamethylene dichloride.

EXAMPLE H.PRODUCTION OF COMPOUND 8 Proceed as in Example A except that equimo- 1, are used. That produces-Compound 8-' where-- R is hydrogen. To produce other compounds responding to the general formula of Compound 8 (see above) use eguimolecular proportions of the and OH, respectively.

I.-PROZDUCTION on COMPOUND-9- Pi'oceed as Example A using-equihioleciilar pro ortions of his (betw cm ii 3mm That' pioduces' Compound 9 where R" the general formula of Compound 9 use equimolecular proportions of N-substituted bis (be a chlor'othyll amines where R is 'analkyl; aryl or aralkyl radical;

The yield of ring compound as obtamed by distillation ofwashed polmer latex. in some: cases is quite small. This yield may be increased in anycase by the additionfof'a amount of 3 sodium-hydroxide to the latex. The quantity of hydroxide or other strong hydroxides, such as potassium, required for this purpose, may vary from to 25 molar-per cent but is advantageously usedbetween=% and All of these polymers prepared. as above described, and also the polymers from other halides similarly prepared, have been found to yieldthese cyclic materials. In many cases extremely small quantities are found,- the quantity being so small that it is necessary to extract the cyclic material from the clear distillate. However, all of the cyclic materials possess this capability of repolymerization to the polymer from which they have been prepared and this polymerization will take place spontaneously unless all traces of moisture or catalyzing influences are carefully removed. Samples which have been carefully purified in respect to moisture and catalyzing influences are capable of indefinite storage in glass.

In the above manner, polymeric C2H4Sz yielded on steam distillation a powder in the distillate. This resulted from the cyclic material presumably originally present. If benzene is added to the distilling flask as the distillation proceeds, the distillate contains dissolved in the benzene an extremely small amount of oil possessing a strong unpleasant odor which very rapidly polymerizes to a powder resembling the original ethylene disulfide polymer. In this case it has proved up to the present time impossible to isolate any of the monomeric 4 membered dimethylene disulfide ring.

Trimethylene disulfide distills, in the procedure of Example H, at a very fast rate but polymerizes in the condenser to give a paper-like cast unless benzene is fed into the system. If benzene is fed in, as above described, there is obtained a yellow distillate which on drying is stable for a few hours. In this case the 5 membered trimethylene disulfide ring originally present polymerizes very rapidly to a paper-like polymer i. e., hard and brittle polymer. It could not be obtained free from the benzene.

2-methyl trimethylene disulfide distills, in the procedure of Example H, over at a very fast rate to give a yellow oil with slightly better stability than that of the straight trimethylene disulfide. The oil may be obtained and has a powerful unpleasant odor. It polymerizes quite rapidly to give a hard horn-like material.

2-hydroxy trimethylene disulfide distills, in the procedure of Example H, yielding the ring ma- I rsf-lrxyd-ro gens Toproduce other compounds responding to 10 terialat a--fairly'-good rate asa' pale yellowoil which can-be isolated'. Samples so far obtainedhavenot-been very stable but presumably could be stabilized if necessary 'byextreme desiccation.

Thisoil 'polymerizes quite rapidlybut in thiscase gives most unexpectedly-a crystal-line struc-- ture"-in-the -resul-tirrg polymeri-n spite of the-fact" that said polymer thus obtained is'a soft wax-like materiaL (C2H4SC'2I-I4S2) obtained as in Example B distills easily giving a fairly good yield Of a pale colored oil which when dried apparently has complete stability. It polymerizes fairly slowly if a trace of moisture'is'presentor'quite rapidly with suitable catalysts. On polymerization it gives a tough horn-like material.

(C2I-I4OCZH4S2) obtained as in Example A above distills with steam yielding anoil. at-a fairly good- (C2I-I4OC2H4S4) behaves"- in almost all respects the same as the corresponding disulfideipolymer yielding apparently the same" oil, but at a slower 1 rate.

(C2H4OCH2O'C2H4S2') onsteam distillation gives a distillate which is colorless and perfectly cigar.

From this solution by ether extraction-there, is

obtainable a very paleyellow oil which if dry has good stability and-whichmay. bepol-ynrerized with water or other catalysts to a rubber. This ability to polymerize in the presence of water is very nicely demonstrated by this material since if the distillate is allowed to stand over-night it becomes milky and the polymer will settle out as a skin or powder in the bottom of the flask.

(02H4OC2H4OC2H4S2) likewise distills to give a clear solution in the distillate. On standing it likewise will deposit a small amount of polymer. If, however, the solution is extracted with ether shortly after distillation there is obtained then an extremely small amount of an oil with a slight color. This oil apparently crystallizes at a temperature only slightly below room temperature and its condition as an oil or solid is dependent on the temperature.

The above represents a number of examples of materials of this type obtained by this method. All of the polysulfide polymers so far distilled have given varying amounts of similar compounds in the distillate, the yield in some cases being only a few hundredths of a per cent.

It has been found that the rate of formation of the monomeric disulfides is faster when dry distillation is used instead of steam distillation. An example of dry distillation is as follows.

EXAMPLE K A poly thio polymercaptan prepared in accordance with U. S. Patent 2,466,963, issued April 12, 1949, to Patrick et al., and having a molecular weight of about 2,000 to 25,000 is mixed with 5 to 75 per cent by weight of a caustic alkali e. g. KOH or NaOH. The mixture is heated at pressures of about 0.1 mm. to 20.0 mm. and temperatures of 50 C. to 500 C. until the distillation of the monomeric disulfide slows to an inappreciable rate. In an illustrative example i. e. where the polymeric unit is SC2I-I4OC2H4S-- the yield of corresponding monomeric disulfide was 51 per cent by weight in about two hours of distillation as compared with about one month to obtain the same yield by steam distillation.

Polysulfide polymers in general can be thus treated i. e. polysulfide polymers comprising recurring units selected from the group consisting of SRS- and R'(S):c where S is a sulfur atom, R is a radical having a sulfur-connected valence of two and R is a radical having a sulfur connected valence equal to a: where a: is a whole number greater than two, said radicals being selected from the groups consisting of designating a single carbon atom designating two adjacent carbon atoms and designating two carbon atoms joined to and separated by intervening structure.

This application is a continuation-in-part of my copending application Serial N0. 50,011, filed September 18, 1948, entitled Disulfide Ring Compounds and Polymerization Thereof, now abancloned.

The phase thus treated in lines 1 and 2, column 11 means treated by the process of dry distillation and also steam distillation.

12 What is claimed is: Process which comprises treating a monomeric disulfide having the general formula where Z is a member of the group consisting of O, S, OCH2O, SCH2S, -OC2H4O, SC2H4S--, and CH2- with from 0.05 to 10 percent of a catalyst of the group consisting of alkali alcoholates, ammonia, alkyl and aralkyl substituted ammonia compounds, alkyl and aralkyl substituted ammonium compounds, and a1- kaline sulfides, hydrosulfides and polysulfides.

OTHER REFERENCES Beilstein: Handbuch der Organischen Chemie, vol. 19, pages 433, 434 (1934).

Ray: Jour. Chem. Soc. (London), vol. 117, pages 1090-1092, 1920.

Fromm: Ber. der Deutschen Chem. GeselL, vol. 58, pages 304-309 (1925). 

